JP2014118370A - Method of manufacturing polymethoxyflavones - Google Patents
Method of manufacturing polymethoxyflavones Download PDFInfo
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- JP2014118370A JP2014118370A JP2012273185A JP2012273185A JP2014118370A JP 2014118370 A JP2014118370 A JP 2014118370A JP 2012273185 A JP2012273185 A JP 2012273185A JP 2012273185 A JP2012273185 A JP 2012273185A JP 2014118370 A JP2014118370 A JP 2014118370A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
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- ULSUXBXHSYSGDT-UHFFFAOYSA-N tangeretin Chemical compound C1=CC(OC)=CC=C1C1=CC(=O)C2=C(OC)C(OC)=C(OC)C(OC)=C2O1 ULSUXBXHSYSGDT-UHFFFAOYSA-N 0.000 claims description 11
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- MRIAQLRQZPPODS-UHFFFAOYSA-N nobiletin Chemical compound C1=C(OC)C(OC)=CC=C1C1=CC(=O)C2=C(OC)C(OC)=C(OC)C(OC)=C2O1 MRIAQLRQZPPODS-UHFFFAOYSA-N 0.000 claims description 5
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- IECRXMSGDFIOEY-UHFFFAOYSA-N Tangeretin Natural products COC=1C(OC)=C(OC)C(OC)=C(C(C=2)=O)C=1OC=2C1=CC=C(O)C=C1 IECRXMSGDFIOEY-UHFFFAOYSA-N 0.000 claims description 4
- DGPHAUBUAGDZCS-UHFFFAOYSA-N 2-(2,3-dimethoxyphenyl)-3,5,6,7,8-pentamethoxychromen-4-one Chemical compound COC1=CC=CC(C2=C(C(=O)C3=C(OC)C(OC)=C(OC)C(OC)=C3O2)OC)=C1OC DGPHAUBUAGDZCS-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Preparation Of Fruits And Vegetables (AREA)
- Seasonings (AREA)
- Pyrane Compounds (AREA)
Abstract
Description
本発明は、水溶性で保存安定性に優れた高純度のポリメトキシフラボン類を、天然物を原材料として製造する方法に関するものである。
詳しくは、みかん属植物の果皮や種などを原材料とし、超臨界二酸化炭素流体と助溶媒であるエタノール水溶液とを用いて得られた抽出物から、濃縮による溶媒の除去と液液抽出、多孔質素材を用いた精製工程により、保存安定性に優れた水溶性ポリメトキシフラボン類を製造する方法に関する。
The present invention relates to a method for producing high-purity polymethoxyflavones having water-solubility and excellent storage stability using natural products as raw materials.
Specifically, the removal of the solvent by concentration, liquid-liquid extraction, and porosity from the extract obtained from the skin and seeds of the mandarin orange plant, using a supercritical carbon dioxide fluid and an aqueous ethanol solution as a cosolvent The present invention relates to a method for producing water-soluble polymethoxyflavones having excellent storage stability by a purification process using raw materials.
従来から下記一般式(I)
の構造式で表されるポリメトキシフラボン類は、みかん属植物、すなわち柑橘類に多く含まれていることが知られている。
特にノビレチン(上記式(I)でR1、R2、R3、R4、及びR5のすべてがメトキシ基)に関しては、発ガン抑制作用等の生理活性が明らかにされている物質である(非特許文献1参照)。
Conventionally, the following general formula (I)
It is known that polymethoxyflavones represented by the structural formula are contained in a large amount in mandarin orange plants, that is, citrus fruits.
In particular, nobiletin (in the above formula (I), R 1 , R 2 , R 3 , R 4 , and R 5 are all methoxy groups) is a substance whose physiological activity such as carcinogenesis-inhibiting action has been clarified. (Refer nonpatent literature 1).
さらにポリメトキシフラボン類は食品の分野において、呈味改善剤及び呈味改善方法(特許文献1参照)や、香味劣化抑制剤(特許文献2参照)など、様々な有用な効果が見出され注目されている。 Furthermore, polymethoxyflavones have been found to have various useful effects such as a taste improving agent and a taste improving method (see Patent Document 1) and a flavor deterioration inhibitor (see Patent Document 2) in the field of food. Has been.
みかん属植物の果皮油にはポリメトキシフラボン類以外に、性質が非常に異なる多種多様な数多くの成分が含まれている(非特許文献2、非特許文献3参照)。例えば、テルペン類等の炭化水素化合物、アルデヒド、エステル等のカルボニル化合物、アルコール類等の揮発性成分および通常の条件では揮発しないワックス類、カロテノイド色素等の不揮発性成分が含まれており、簡便な方法でポリメトキシフラボン類を選択的に分離することは困難とされている。 In addition to polymethoxyflavones, the peel oil of the mandarin orange genus plant contains a large variety of components with very different properties (see Non-patent Documents 2 and 3). For example, it contains hydrocarbon compounds such as terpenes, carbonyl compounds such as aldehydes and esters, volatile components such as alcohols, and non-volatile components such as waxes and carotenoid pigments that do not volatilize under normal conditions. It is difficult to selectively separate polymethoxyflavones by the method.
みかん属植物に含まれるポリメトキシフラボン類を精製する従来技術が、前掲の特許文献1及び2に開示されている。
具体的には、みかん属植物の果実、果皮、果皮油、種、葉部等の原料からエタノールやメタノール、クロロホルム等の有機溶剤を用いて加熱抽出する方法や、それらの抽出方法と合成樹脂による精製を組み合わせた方法である。
Conventional techniques for purifying polymethoxyflavones contained in mandarin orange plants are disclosed in Patent Documents 1 and 2 described above.
Specifically, it is a method of heat extraction from raw materials such as fruit, pericarp, pericarp oil, seeds, leaves, etc. of mandarin orange plants using an organic solvent such as ethanol, methanol, chloroform, etc. This method combines purification.
また超臨界流体と助溶媒を併用して抽出する方法(特許文献3参照)や抽出した果皮油から分子蒸留を用いて分離精製する方法(特許文献4、特許文献5参照)なども知られている。 Also known are a method of extraction using a supercritical fluid and a cosolvent in combination (see Patent Document 3), a method of separating and purifying the extracted peel oil using molecular distillation (see Patent Document 4 and Patent Document 5), and the like. Yes.
前掲の特許文献4及び5記載の分子蒸留を用いる方法では、確かにポリメトキシフラボン類を精製する上で有効であると考えられる。しかし、精留及び分子蒸留といった蒸留操作を繰り返し行わなければならず、工程が煩雑で長いため時間あたりの収率が悪く、また長い熱履歴による精油の劣化などが懸念される。さらに原料には精油しか使用できないため、まず精油を得る工程も必要となってくる。 The methods using molecular distillation described in the above-mentioned Patent Documents 4 and 5 are certainly considered to be effective in purifying polymethoxyflavones. However, distillation operations such as rectification and molecular distillation must be repeated, and the process is complicated and long, so the yield per hour is poor, and there is a concern that the essential oil deteriorates due to a long heat history. Furthermore, since only essential oil can be used as a raw material, a process for obtaining essential oil is also required.
そこで原料の形態にとらわれることなく、短時間で効率良くポリメトキシフラボン類を得る方法として前掲の特許文献3に記載されているような超臨界流体と助溶媒を用いて抽出する方法が挙げられる。当該方法において、超臨界流体として一般的に利用されている二酸化炭素を用いれば、原料に対する熱履歴などの不安も少なく安全且つ省エネルギーで抽出することが可能である。 Therefore, as a method for efficiently obtaining polymethoxyflavones in a short time without being limited by the form of the raw material, there is a method of extraction using a supercritical fluid and a cosolvent as described in Patent Document 3 mentioned above. In this method, if carbon dioxide, which is generally used as a supercritical fluid, is used, the extraction can be performed safely and energy-saving with less anxiety such as a heat history of the raw material.
しかし上記の特許文献3の方法で得られる抽出物は、助溶媒由来のエタノール水溶液と原料由来の炭化水素化合物をはじめとする非極性の油脂成分からなる不均一な液体である。また目的のポリメトキシフラボン類の純度もあまり高いものではなく、そのままでは呈味改善剤や香味劣化抑制剤等の目的で食品等に使用する上で極めて用途が制限されることとなる。 However, the extract obtained by the method of Patent Document 3 is a heterogeneous liquid composed of nonpolar oil and fat components including an aqueous ethanol solution derived from a co-solvent and a hydrocarbon compound derived from a raw material. In addition, the purity of the target polymethoxyflavones is not so high, and as such, the use thereof is extremely limited for use in foods and the like for purposes such as taste improvers and flavor deterioration inhibitors.
前掲の特許文献3においては、上記のような抽出物を濃縮し、その濃縮物をエタノールに溶解させることで分析サンプルを供する方法が示されている。
しかしながら、この方法で得られる組成物中には原料由来の油脂成分が多く含まれているためポリメトキシフラボン類の純度は低く、食品などに添加物として使用するには不向きである。また濃縮物そのものの極性が低いため、特に水溶性のものが求められる飲料などにはそのまま使用することが出来ない。
In the above-mentioned Patent Document 3, a method of providing an analytical sample by concentrating the extract as described above and dissolving the concentrate in ethanol is shown.
However, since the composition obtained by this method contains a large amount of oil and fat components derived from raw materials, the purity of polymethoxyflavones is low and is unsuitable for use as an additive in foods and the like. Further, since the polarity of the concentrate itself is low, it cannot be used as it is, particularly for beverages that require water-soluble products.
本発明の目的は、超臨界流体抽出によって得られたみかん属植物の抽出物から、保存安定性と水溶性に優れたポリメトキシフラボン類を高純度で製造する方法を提供することである。 An object of the present invention is to provide a method for producing polymethoxyflavones excellent in storage stability and water solubility with high purity from an extract of a mandarin orange plant obtained by supercritical fluid extraction.
本発明者らは、上記製造方法を確立するために鋭意研究した結果、下記の方法で、水溶性の安定なポリメトキシフラボン類を高い純度で簡便に製造できることを見出し、本発明を完成するに至った。
本発明の方法では、まず、超臨界流体と助溶媒によって得られた抽出物から濃縮操作に
よりエタノール水溶液を除去しオイル様の濃縮物とする。次いで、得られたオイル様の濃縮物に新たにエタノール水溶液を加えて液液抽出を行い、その後活性炭などの多孔質素材で精製する。そして最後にエタノール濃度及び固形濃度の調整を行う。
As a result of intensive studies to establish the above production method, the present inventors have found that water-soluble stable polymethoxyflavones can be easily produced with high purity by the following method, and to complete the present invention. It came.
In the method of the present invention, first, an aqueous ethanol solution is removed from an extract obtained with a supercritical fluid and a cosolvent by a concentration operation to obtain an oil-like concentrate. Next, an aqueous ethanol solution is newly added to the obtained oil-like concentrate to perform liquid-liquid extraction, and then purified with a porous material such as activated carbon. Finally, the ethanol concentration and solid concentration are adjusted.
本発明は、超臨界流体と助溶媒によって得られた抽出物を濃縮により助溶媒を除去した後、液液抽出と活性炭処理を行うことによって、安定で水溶性のポリメトキシフラボン類を製造する方法である。
すなわち、本発明は、下記の工程:
(A)超臨界流体と助溶媒による抽出操作によって、みかん属植物から抽出液Aを得る工程;
(B)濃縮操作によって、前記抽出液Aから助溶媒を除去した濃縮物Bを得る工程;
(C)エタノール水溶液による抽出操作によって、前記濃縮物Bから抽出液Cを得る工程;
(D)前記抽出液C又は前記抽出液Cにエタノール水溶液を添加した希釈溶液を多孔質素材で精製してポリメトキシフラボン類を得る工程;
を含む、水溶性ポリメトキシフラボン類の製造方法である。
The present invention relates to a method for producing stable and water-soluble polymethoxyflavones by performing liquid-liquid extraction and activated carbon treatment after removing a co-solvent by concentrating an extract obtained with a supercritical fluid and a co-solvent. It is.
That is, the present invention includes the following steps:
(A) A step of obtaining an extract A from a mandarin plant by extraction with a supercritical fluid and a cosolvent;
(B) The process of obtaining the concentrate B which removed the cosolvent from the said extract A by concentration operation;
(C) A step of obtaining an extract C from the concentrate B by an extraction operation with an aqueous ethanol solution;
(D) A step of purifying the extract C or a diluted solution obtained by adding an aqueous ethanol solution to the extract C with a porous material to obtain polymethoxyflavones;
Is a process for producing water-soluble polymethoxyflavones.
本発明の製造方法によれば、水に対する溶解性が高く、かつ長期間保存した場合に溶解後の沈殿や濁りが生じることのない安定性に優れたポリメトキシフラボン類を簡便で経済的に得ることができる。また、本発明の製造方法によれば、純度が高く異味異臭のないポリメトキシフラボン類を提供することができる。 According to the production method of the present invention, polymethoxyflavones that are highly water-soluble and have excellent stability that does not cause precipitation or turbidity after dissolution when stored for a long period of time are obtained simply and economically. be able to. Moreover, according to the production method of the present invention, polymethoxyflavones having high purity and no off-flavor can be provided.
以下に本発明の実施形態について説明する。
〔1〕ポリメトキシフラボン類およびその原材料
本発明で製造されるポリメトキシフラボン類は、下記一般式(I):
具体的には、ペンタメトキシフラボン(融点179℃)、ノビレチン(融点134℃)、テトラメトキシフラボン(融点128℃)、ヘプタメトキシフラボン(融点129〜131℃)、タンゲレチン(融点154℃)等が該当する。
Embodiments of the present invention will be described below.
[1] Polymethoxyflavones and raw materials thereof The polymethoxyflavones produced in the present invention have the following general formula (I):
Specifically, pentamethoxyflavone (melting point 179 ° C), nobiletin (melting point 134 ° C), tetramethoxyflavone (melting point 128 ° C), heptamethoxyflavone (melting point 129 to 131 ° C), tangeretin (melting point 154 ° C), and the like To do.
上記ポリメトキシフラボン類は、みかん属(Citrus)植物の外果皮に含まれる果皮油中に多く含有されている。中でも、入手の容易さの観点から特にシイクワシャー(Citrus depressa Hayata)、スイートオレンジ(Citrus sinensis)、サワーオレンジ(Citrus aurantium)、タンジェリン(Citrus reticlata Blanco var. tangerine)、マンダリン(Citrus reticlata Blanco var. mandarin)の果皮を原材料として用いることが好ましい。
果皮の形態は特に限定されるものではないが、例えば、果汁を搾汁した後の残渣を生の
ままもしくは乾燥したものを使用する方法が挙げられる。
The polymethoxyflavones are contained in a large amount in the peel oil contained in the outer peel of Citrus plants. Among these, from the viewpoint of easy availability, Shikuwasha (Citrus depressa Hayata), sweet orange (Citrus sinensis), sour orange (Citrus aurantium), tangerine (Citrus reticlata Blanco var. Tangerine), mandarin (Citrus reticlata Blanco var. Mandarin) It is preferable to use as a raw material.
Although the form of a fruit skin is not specifically limited, For example, the method of using what dried the residue after squeezing fruit juice raw or dried is mentioned.
〔2〕超臨界流体による抽出工程(工程A)
本工程で使用する超臨界流体としては、例えば、その圧力が7.4〜60MPa、好ましくは15〜40MPa、その温度が32〜100℃、好ましくは35〜70℃の領域における超臨界状態の二酸化炭素が挙げられる。また使用する超臨界流体の使用量は原料のみかん属植物の1〜3倍容量、好ましくは1.7〜2.5倍容量であり、その抽出時間は、2〜6時間、好ましくは2.5〜4時間である。
[2] Extraction process with supercritical fluid (process A)
As the supercritical fluid used in this step, for example, the pressure is 7.4 to 60 MPa, preferably 15 to 40 MPa, and the temperature is 32 to 100 ° C., preferably 35 to 70 ° C. Carbon. The amount of supercritical fluid to be used is 1 to 3 times, preferably 1.7 to 2.5 times the volume of the raw mandarin plant, and the extraction time is 2 to 6 hours, preferably 2. 5 to 4 hours.
さらに本発明ではポリメトキシフラボン類の抽出効率を上げるため、上記超臨界流体と共に助溶媒を使用することが好ましい。助溶媒としてはエタノール水溶液が食品に使用できる観点から好適である。そのエタノール濃度は10〜80(w/w)%、好ましくは20〜50(w/w)%である。使用量は原料のみかん属植物の0.1〜2倍、好ましくは0.3〜1倍量である。 Furthermore, in the present invention, in order to increase the extraction efficiency of polymethoxyflavones, it is preferable to use a co-solvent together with the supercritical fluid. As the cosolvent, an aqueous ethanol solution is preferable from the viewpoint that it can be used in foods. The ethanol concentration is 10 to 80 (w / w)%, preferably 20 to 50 (w / w)%. The amount used is 0.1 to 2 times, preferably 0.3 to 1 times the amount of the raw mandarin plant.
〔3〕濃縮工程(工程B)
本工程は、先の超臨界流体抽出によって得られた抽出物中の助溶媒、例えばエタノール水溶液を、エバポレーター等を用いた濃縮操作によって除去する工程である。
みかん属植物の果皮等から超臨界二酸化炭素流体と助溶媒であるエタノール水溶液で抽出物を得た場合、その抽出物は、水溶性ポリメトキシフラボン類が多量に存在する含水エタノール抽出液とみかん属植物の果皮由来のオイル抽出液の不均一な溶液となる。ここで抽出液中のエタノール水溶液のみを分離、精製することでポリメトキシフラボン類の液体製剤とすることも可能であるが、不要な非極性成分を多く含むため飲料などに添加する際、沈殿や濁りなどを生じてしまい安定な水溶性製剤であるとは言えない。
また、分離した含水エタノール抽出液は高アルコール濃度であるため、水を加えて低アルコール濃度に調整して不要成分を除去し精製する方法も考えられる。しかし、この方法による調整液は白濁化しているため、活性炭処理などで清澄化することは可能であるが、その際ポリメトキシフラボン類も多く失われるため有効な方法とは言えない(後記の比較例1を参照)。
[3] Concentration step (Step B)
This step is a step of removing the co-solvent in the extract obtained by the previous supercritical fluid extraction, for example, an ethanol aqueous solution, by a concentration operation using an evaporator or the like.
When an extract is obtained from the skin of a mandarin orange plant with a supercritical carbon dioxide fluid and an aqueous ethanol solution as a co-solvent, the extract is a hydrous ethanol extract containing a large amount of water-soluble polymethoxyflavones and a mandarin genus. It becomes a non-uniform solution of the oil extract derived from the skin of the plant. Here, it is possible to obtain a liquid preparation of polymethoxyflavones by separating and purifying only the ethanol aqueous solution in the extract, but since it contains a lot of unnecessary nonpolar components, It cannot be said that it is a stable water-soluble preparation due to turbidity.
Further, since the separated water-containing ethanol extract has a high alcohol concentration, a method of adding water to adjust to a low alcohol concentration to remove unnecessary components and purify can also be considered. However, since the adjustment liquid by this method is clouded, it can be clarified by activated carbon treatment, etc., but at that time, a lot of polymethoxyflavones are lost, so it cannot be said that it is an effective method (comparison described later). (See Example 1).
そこで含水エタノール抽出液中の各成分を一旦オイル抽出液に移行させ、改めてポリメトキシフラボン類を含む成分を精製抽出する必要がある。すなわちエタノール及び水を濃縮操作により除去することで、次工程でのポリメトキシフラボン類の精製抽出を可能とするものである。
また、濃縮後の助溶媒の濃度は、例えば助溶媒がエタノールである場合は、濃縮物中に0〜10(w/w)%が好ましく、特に好ましくは0〜5(w/w)%である。
Therefore, it is necessary to transfer each component in the water-containing ethanol extract to the oil extract once, and again purify and extract the component containing polymethoxyflavones. That is, by removing ethanol and water by a concentration operation, it is possible to purify and extract polymethoxyflavones in the next step.
The concentration of the co-solvent after concentration is preferably 0 to 10 (w / w)%, particularly preferably 0 to 5 (w / w)% in the concentrate when the co-solvent is ethanol, for example. is there.
〔4〕液液抽出工程(工程C)
上記濃縮物からポリメトキシフラボン類を効率よく精製抽出する簡便な方法としてエタノール水溶液を用いた液液抽出が挙げられる。
その際、エタノール濃度はなるべく低い方が不要な油溶成分を抽出することなくポリメトキシフラボン類を抽出することができるが、あまり低すぎるとポリメトキシフラボン類の抽出効率を損なうこととなる。そのため抽出に使用するエタノール水溶液の濃度は10〜80(w/w)%、好ましくは20〜40(w/w)%である。
使用量は濃縮物の2〜40倍、好ましくは5〜20倍量である。また抽出時の温度は、10〜90℃、好ましくは40〜80℃である。
[4] Liquid-liquid extraction process (Process C)
A simple method for efficiently purifying and extracting polymethoxyflavones from the concentrate is liquid-liquid extraction using an aqueous ethanol solution.
At that time, when the ethanol concentration is as low as possible, polymethoxyflavones can be extracted without extracting unnecessary oil-soluble components. However, when the ethanol concentration is too low, the extraction efficiency of polymethoxyflavones is impaired. Therefore, the concentration of the aqueous ethanol solution used for extraction is 10 to 80 (w / w)%, preferably 20 to 40 (w / w)%.
The amount used is 2 to 40 times, preferably 5 to 20 times that of the concentrate. Moreover, the temperature at the time of extraction is 10-90 degreeC, Preferably it is 40-80 degreeC.
〔5〕濃度調整工程(工程C1)
上記液液抽出によって得られた抽出液は、そのまま次の工程Dに付することができるが、濃度調整の観点から、次工程Dの実施前に、エバポレーター等で、水及びエタノールを
除去して濃縮し、エタノール濃度調整を行うことが好ましい。調整後のエタノール濃度は、40〜90(w/w)%が好ましく、特に好ましくは50〜80(w/w)%である。
[5] Concentration adjustment process (process C1)
The extract obtained by the liquid-liquid extraction can be directly applied to the next step D, but from the viewpoint of concentration adjustment, water and ethanol are removed with an evaporator or the like before the next step D is performed. It is preferable to concentrate and adjust the ethanol concentration. The ethanol concentration after adjustment is preferably 40 to 90 (w / w)%, particularly preferably 50 to 80 (w / w)%.
〔6〕精製工程(工程D)
工程C1を省略する場合は、工程Cで得られた抽出液をそのまま、或いは工程Cの抽出液にエタノール水溶液を添加することにより希釈した希釈溶液を精製処理に付する。
工程C1を実施する場合は、工程C1で得られた溶液にエタノール水溶液を添加して希釈した後、当該希釈溶液を精製処理に付する。
多孔質素材による精製処理に付す際の溶液濃度は、ポリメトキシフラボン濃度が0.1〜20質量%、特に5質量%程度が好ましく、また、エタノール濃度が20〜100質量%、特に70質量%程度に調整しておくことが好適である。
必要に応じて上記の濃度の調整を行った後、当該溶液を多孔質素材によって精製し、より安定なポリメトキシフラボン類を得ることができる。
多孔質素材による精製は、通常行われている方法で行えば良く、例えば、カラムに充填された多孔質素材に前記抽出物を含む溶液を一定流量で接触させる方法や、該抽出物に多孔質素材を投入し、一定時間撹拌後に多孔質素材を分離する方法がある。その方法に格別の制約はなく、目的により選択することができる。
[6] Purification step (Step D)
When omitting step C1, the diluted solution obtained by diluting the extract obtained in step C as it is or by adding an aqueous ethanol solution to the extract of step C is subjected to purification treatment.
When implementing the step C1, after diluting the solution obtained in the step C1 with an aqueous ethanol solution, the diluted solution is subjected to purification treatment.
The concentration of the solution used for the purification treatment with the porous material is preferably a polymethoxyflavone concentration of 0.1 to 20% by mass, particularly preferably about 5% by mass, and an ethanol concentration of 20 to 100% by mass, particularly 70% by mass. It is preferable to adjust to the extent.
After adjusting the concentration as necessary, the solution can be purified with a porous material to obtain more stable polymethoxyflavones.
Purification using a porous material may be performed by a commonly used method, for example, a method in which a solution containing the extract is brought into contact with a porous material packed in a column at a constant flow rate, or the extract is porous. There is a method of putting a raw material and separating a porous material after stirring for a certain time. There is no particular restriction on the method, and it can be selected according to the purpose.
使用できる多孔質素材は、活性炭もしくは非イオン性多孔性樹脂吸着剤が安価で簡便に使用できる点で好ましい。
樹脂吸着剤は、一般に不溶性の三次元架橋構造ポリマーであってイオン交換基のような官能基を実質的に持たないものであり、例えば、その母体がスチレン系である「アンバーライト(登録商標)XAD−16」(オルガノ株式会社製)、スチレン−ジビニルベンゼン共重合体系である「セパビーズSP70(商品名)」(三菱化学株式会社製)あるいは「ダイヤイオンHP20(商品名)」(三菱化学株式会社製)等を使用できるが、これらに限るものではない。
The porous material that can be used is preferable in that activated carbon or nonionic porous resin adsorbent is inexpensive and can be used easily.
The resin adsorbent is generally an insoluble three-dimensional crosslinked structure polymer and substantially free of a functional group such as an ion exchange group. For example, “Amberlite (registered trademark)” whose matrix is styrene-based is used. "XAD-16" (manufactured by Organo Corporation), "Separbeads SP70 (trade name)" (Mitsubishi Chemical Corporation) or "Diaion HP20 (trade name)" (Mitsubishi Chemical Corporation), which is a styrene-divinylbenzene copolymer system However, it is not limited to these.
多孔質素材の使用量はその種類によっても異なるが、処理液中の固形に対して、5〜100(w/w)%量、好ましくは10〜50(w/w)%量である。また処理時の温度は、0〜90℃、好ましくは20〜70℃である。さらに処理時間は、0.5〜10時間、好ましくは1〜5時間である。
なお、抽出液に多孔質素材を投入した場合は、処理後にメッシュろ過、ろ紙ろ過又は珪藻土ろ過など一般的なろ過方法によって使用した多孔質素材を除去することが出来る。
Although the usage-amount of a porous raw material changes also with the kind, it is 5-100 (w / w)% amount with respect to solid in a processing liquid, Preferably it is 10-50 (w / w)% amount. Moreover, the temperature at the time of a process is 0-90 degreeC, Preferably it is 20-70 degreeC. Further, the treatment time is 0.5 to 10 hours, preferably 1 to 5 hours.
In addition, when a porous material is added to the extract, the porous material used can be removed by a general filtration method such as mesh filtration, filter paper filtration, or diatomaceous earth filtration after the treatment.
〔7〕ポリメトキシフラボン類の製剤化
得られたポリメトキシフラボン類は、高純度のペンタメトキシフラボン、ノビレチン、テトラメトキシフラボン、ヘプタメトキシフラボン及びタンゲレチンから成るので、そのままでも飲食品などに添加して使用できるが、必要に応じて、公知の製剤添加剤などと混合して、カプセル、顆粒状、錠剤、ペースト状又は飲料の形態に製剤化することができる。
[7] Formulation of polymethoxyflavones The resulting polymethoxyflavones are composed of high-purity pentamethoxyflavone, nobiletin, tetramethoxyflavone, heptamethoxyflavone and tangeretin. Although it can be used, if necessary, it can be mixed with a known formulation additive and the like, and can be formulated into a capsule, granule, tablet, paste or beverage form.
公知の製剤添加剤としては、賦形剤、基剤、結合剤、崩壊剤、崩壊補助剤、滑沢剤、流動化剤、コーティング剤、可塑剤、消泡剤、糖衣剤、剤皮、光沢化剤、発泡剤、防湿剤、界面活性剤、可溶化剤、緩衝剤、溶解剤、溶解補助剤、溶剤、安定化剤、乳化剤、懸濁剤、分散剤、抗酸化剤、充填剤、粘稠剤、粘稠化剤、pH調整剤、防腐剤、保存剤、甘味剤、矯味剤、清涼化剤、着香剤・香料、芳香剤、着色剤などが挙げられる。 Known formulation additives include excipients, bases, binders, disintegrants, disintegration aids, lubricants, fluidizing agents, coating agents, plasticizers, antifoaming agents, dragees, skins, gloss Agent, foaming agent, moisture-proofing agent, surfactant, solubilizer, buffering agent, solubilizer, solubilizer, solvent, stabilizer, emulsifier, suspending agent, dispersant, antioxidant, filler, viscosity Examples include thickeners, thickeners, pH adjusters, preservatives, preservatives, sweeteners, flavoring agents, refreshing agents, flavoring agents / fragrances, fragrances, and coloring agents.
また、その他、DHA(ドコサヘキサエン酸)、EPA(エイコサペンタエン酸)、ホスファチジルセリン、ホスファチジルコリン、大豆レシチン、卵黄レシチン、トコトリエノール、GABA(γ−アミノ酪酸)、テアニン、リコピン、ヤマブシタケ、イチョウ葉
、明日葉、ホップ、菊の花、ガジュツ、サフラン、ニンニク、発芽玄米、ビタミンC、ビタミンE、コエンザイムQ10、ローヤルゼリー、プロポリス、コラーゲン、植物ステロール、植物性油脂類(オリーブ油、大豆油など)、不飽和脂肪酸、ミツロウ、亜鉛酵母、セレン酵母等を配合してもよい。
In addition, DHA (docosahexaenoic acid), EPA (eicosapentaenoic acid), phosphatidylserine, phosphatidylcholine, soybean lecithin, egg yolk lecithin, tocotrienol, GABA (γ-aminobutyric acid), theanine, lycopene, yamabushitake, ginkgo biloba, tomorrow, Hops, chrysanthemum flowers, gadgets, saffron, garlic, germinated brown rice, vitamin C, vitamin E, coenzyme Q10, royal jelly, propolis, collagen, plant sterols, vegetable oils and fats (olive oil, soybean oil, etc.), unsaturated fatty acids, beeswax Zinc yeast, selenium yeast, etc. may be blended.
以下に実施例を挙げて本発明を具体的に説明するが、本発明は実施例の記載に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the description of the examples.
〔実施例1〕
(1)試料
シイクワシャーの果皮及び種を熱風機械乾燥し、ハンマーミルで粉砕したものを試料とした。
[Example 1]
(1) Sample A sample obtained by drying the skin and seeds of Shikuwasha with hot air machine and pulverizing with a hammer mill was used.
(2)超臨界流体による抽出
試料約250gに50(w/w)%エタノールを180g添加し、混合したものを抽出槽に仕込み、圧力25MPa、温度40℃の超臨界二酸化炭素を連続的に4時間供給して抽出を行った。
抽出槽から流出する抽出物含有超臨界二酸化炭素は、圧力4MPa、温度25℃に保った分離槽に移し、抽出物を二酸化炭素から分離し、100gの抽出物を得た。得られた抽出物はエタノール水溶液層とオイル層の2層に分離していた。
(2) Extraction with supercritical fluid 180 g of 50 (w / w)% ethanol was added to approximately 250 g of the sample, and the mixture was charged into an extraction tank, and 4 supercritical carbon dioxides having a pressure of 25 MPa and a temperature of 40 ° C. were continuously added. Extraction was carried out by feeding for hours.
The extract-containing supercritical carbon dioxide flowing out from the extraction tank was transferred to a separation tank maintained at a pressure of 4 MPa and a temperature of 25 ° C., and the extract was separated from the carbon dioxide to obtain 100 g of an extract. The obtained extract was separated into two layers, an aqueous ethanol layer and an oil layer.
(3)濃縮
ロータリーエバポレーターで、上記で得られた抽出物から水及びアルコールを除去し、ほぼオイル層のみになるまで濃縮し、30gの濃縮物を得た。
(3) Concentration With a rotary evaporator, water and alcohol were removed from the extract obtained above, and the mixture was concentrated until almost only an oil layer was obtained, thereby obtaining 30 g of a concentrate.
(4)液液抽出
上記オイル状の濃縮物に30(w/w)%エタノールを300g添加し40℃で2時間攪拌した後、全量を分液ロートに移した。分液ロート中で2時間静置して上下2層に分離させ、下層のエタノール溶液層約300gを抽出液として回収した。回収した抽出液は薄く黄色がかった白濁液の外観を呈していた。
(4) Liquid-liquid extraction After adding 300 g of 30 (w / w)% ethanol to the oily concentrate and stirring at 40 ° C. for 2 hours, the whole amount was transferred to a separatory funnel. The mixture was allowed to stand for 2 hours in a separatory funnel and separated into two upper and lower layers, and about 300 g of the lower ethanol solution layer was recovered as an extract. The recovered extract had a thin yellowish cloudy appearance.
(5)ろ過
上記で得られた抽出液は−15℃で一晩静置し、その後珪藻土ろ過を行った。得られたろ液は清澄化され黄色透明の溶液であった。
(5) Filtration The extract obtained above was allowed to stand at −15 ° C. overnight, followed by diatomaceous earth filtration. The obtained filtrate was clarified and was a yellow transparent solution.
(6)濃度調整及び精製
清澄化されたろ液をロータリーエバポレーターで濃縮し3gの濃縮液を得た。
得られた濃縮液に95(v/v)%エタノールを9.5g、蒸留水を1.5g添加し、ポリメトキシフラボン類を6.5(w/w)%含有する70(w/w)%エタノール溶液に調整した。
この調整液に活性炭を0.3g添加し、65℃で2時間攪拌して精製した後、珪藻土ろ過で活性炭を除去した。その後、水を加えてポリメトキシフラボン類の濃度が5.1(w/w)%になるように調整し、ポリメトキシフラボン類含有液を得た。
(6) Concentration adjustment and purification The clarified filtrate was concentrated with a rotary evaporator to obtain 3 g of a concentrated solution.
9.5 g of 95 (v / v)% ethanol and 1.5 g of distilled water were added to the resulting concentrated liquid, and 70 (w / w) containing 6.5 (w / w)% of polymethoxyflavones. The solution was adjusted to a% ethanol solution.
After adding 0.3g of activated carbon to this adjustment liquid and refine | purifying by stirring at 65 degreeC for 2 hours, activated carbon was removed by diatomaceous earth filtration. Then, water was added and it adjusted so that the density | concentration of polymethoxyflavone might be 5.1 (w / w)%, and the polymethoxyflavone containing liquid was obtained.
こうして製造されたポリメトキシフラボン類含有液は表1に示すように、高純度の各種ポリメトキシフラボンを含んでいた。 As shown in Table 1, the polymethoxyflavone-containing liquid thus produced contained various high-purity polymethoxyflavones.
〔ポリメトキシフラボンの測定〕
各種ポリメトキシフラボンの測定は、得られた水溶性ポリメトキシフラボン類を99.
5%エタノールで1000倍希釈し、高速液体クロマトグラフィー(HPLC)用いて以下の条件で行った。
装置:アジレント・テクノロジー株式会社製「Agilent 1100 HPLC システム」
カラム:株式会社資生堂製「CAPCELL PAK C18MG」
カラム温度:40℃
溶離液:A.アセトニトリル
B.10%アセトニトリル水溶液(pH2.5 H3PO4)
グラジエント条件: 0分 → 25分
A.アセトニトリル 0% 100%
B.10%アセトニトリル水溶液 100% 0%
(pH2.5 H3PO4)
流速:1ml/分間
検出波長:325nm
[Measurement of polymethoxyflavone]
The measurement of various polymethoxyflavones was conducted by measuring the obtained water-soluble polymethoxyflavones 99.
The solution was diluted 1000 times with 5% ethanol and subjected to high performance liquid chromatography (HPLC) under the following conditions.
Equipment: “Agilent 1100 HPLC system” manufactured by Agilent Technologies, Inc.
Column: “CAPCELL PAK C18MG” manufactured by Shiseido Co., Ltd.
Column temperature: 40 ° C
Eluent: A. Acetonitrile
B. 10% acetonitrile aqueous solution (pH 2.5 H 3 PO 4 )
Gradient conditions: 0 minutes to 25 minutes A. Acetonitrile 0% 100%
B. 10% acetonitrile aqueous solution 100% 0%
(PH 2.5 H 3 PO 4 )
Flow rate: 1 ml / min Detection wavelength: 325 nm
ポリメトキシフラボンの含有量は、予め単離した純品で作成した検量線を用いて算出した。
表1の総ポリメトキシフラボン濃度はノビレチンとタンゲレチンの含有濃度の和を示す。また、総固形濃度は、蒸発皿に海砂と水溶性ポリメトキシフラボン類を入れて均一に混合させた後、105℃の恒温槽に2時間入れ、その前後の質量変化で固形量を求めることで算出した。ポリメトキシフラボン純度は、総ポリメトキシフラボン濃度を総固形濃度で除した値を百分率で示した。
The content of polymethoxyflavone was calculated using a calibration curve prepared with a pure product isolated in advance.
The total polymethoxyflavone concentration in Table 1 represents the sum of the concentrations of nobiletin and tangeretin. The total solid concentration should be obtained by mixing sea sand and water-soluble polymethoxyflavones in an evaporating dish and mixing them uniformly, then placing them in a constant temperature bath at 105 ° C. for 2 hours, and determining the solid content by mass change before and after that. Calculated with The polymethoxyflavone purity was expressed as a percentage obtained by dividing the total polymethoxyflavone concentration by the total solid concentration.
実施例1で製造したポリメトキシフラボン類含有液を水に0〜1.0g添加した時のポリメトキシフラボン濃度と比濁度、そして目視で濁っているかを確認した結果を表2に示す。
比濁度はハック社製の比濁計「2100AN型ラボ用濁度計」(ホルマジン標準液)を使用して測定した。
目視評価は、ポリメトキシフラボン類含有液を添加する前の水(透明)を基準に評価した。
この結果からも分かるように、本発明で製造されたポリメトキシフラボン類は水溶性に優れる。
Table 2 shows the polymethoxyflavone concentration and the specific turbidity when 0 to 1.0 g of the polymethoxyflavone-containing liquid produced in Example 1 was added to water, and the results of confirming whether it was cloudy visually.
The turbidity was measured using a turbidimeter “2100AN type turbidimeter for laboratory use” (formazine standard solution) manufactured by Hack.
Visual evaluation was performed based on water (transparent) before adding the polymethoxyflavone-containing liquid.
As can be seen from this result, the polymethoxyflavones produced in the present invention are excellent in water solubility.
実施例1で製造したポリメトキシフラボン類含有液を5℃、25℃、40℃で、2ヶ月、4ヶ月、6ヶ月間保管した後のポリメトキシフラボン濃度の変化や沈殿の発生の有無、異味異臭の発生の有無を確認した結果を表3に示す。表中「0月」は製造直後のポリメトキシフラボン類含有液の状態を示したものである。
この結果からも分かるように、本発明方法で製造されたポリメトキシフラボン類は高い保存安定性を持つものであった。
Changes in polymethoxyflavone concentration, presence or absence of occurrence of precipitation after storage of the polymethoxyflavone-containing liquid prepared in Example 1 at 5 ° C, 25 ° C, and 40 ° C for 2 months, 4 months, and 6 months. Table 3 shows the results of confirming whether or not a strange odor was generated. “October” in the table indicates the state of the polymethoxyflavone-containing liquid immediately after production.
As can be seen from these results, the polymethoxyflavones produced by the method of the present invention have high storage stability.
〔比較例1〕
工程Bの濃縮操作の有効性を確認するため、以下の対比実験を行った。
実施例1の「(2)超臨界流体による抽出」で得られた粗抽出物を濃縮せずにエタノール水溶液層のみを分液ロートにて分離し70gの溶液を得た。得られた溶液の組成は、エタノールが84(w/w)%、水が13(w/w)%、そして固形が3(w/w)%であった。
この溶液に95(v/v)%エタノールを33.1g、水を196.9g添加することで300gに調整した。この調整液は実施例1の「(4)液液抽出」で得られた抽出液と同様に薄く黄色がかった白濁色の外観を呈していた。
その後実施例1の「(5)ろ過」と同様に冷却後、珪藻土ろ過を行ったが溶液は清澄化されず白濁したままだった。
そこで濁りを除去するために活性炭を2g添加し、65℃で2時間攪拌した後、珪藻土ろ過により活性炭を除去した。こうして得られた溶液は黄色透明な外観を呈していた。
この比較例1で得られたポリメトキシフラボン類含有液と実施例1の「(5)ろ過」で得られたポリメトキシフラボン類含有液のそれぞれのポリメトキシフラボン類の濃度及び全固形の濃度、ポリメトキシフラボン類の純度、そしてポリメトキシフラボン濃度が約50ppmとなるように水に添加した時の濁りの有無(目視評価)について表4に示した。
[Comparative Example 1]
In order to confirm the effectiveness of the concentration operation in step B, the following comparison experiment was performed.
Without concentrating the crude extract obtained in “(2) Extraction with supercritical fluid” in Example 1, only the ethanol aqueous solution layer was separated by a separating funnel to obtain 70 g of a solution. The composition of the resulting solution was 84 (w / w)% ethanol, 13 (w / w)% water, and 3 (w / w)% solids.
The solution was adjusted to 300 g by adding 33.1 g of 95 (v / v)% ethanol and 196.9 g of water. Similar to the extract obtained in “(4) Liquid-liquid extraction” in Example 1, this adjustment liquid had a thin yellowish cloudy appearance.
Thereafter, after cooling as in “(5) Filtration” in Example 1, diatomaceous earth filtration was performed, but the solution was not clarified and remained cloudy.
Therefore, 2 g of activated carbon was added to remove turbidity, and the mixture was stirred at 65 ° C. for 2 hours, and then the activated carbon was removed by diatomaceous earth filtration. The solution thus obtained had a yellow transparent appearance.
The polymethoxyflavone-containing liquid obtained in Comparative Example 1 and the polymethoxyflavone-containing liquid obtained in “(5) Filtration” in Example 1, respectively, and the concentration of polymethoxyflavones and the total solid concentration, Table 4 shows the purity of polymethoxyflavones and the presence or absence of turbidity (visual evaluation) when added to water so that the polymethoxyflavone concentration is about 50 ppm.
表4から明らかなように、ポリメトキシフラボン類を効率よく精製抽出し、且つ飲料に添加した際に濁りを生じないようにするためには、実施例1のように超臨界抽出物中のエタノール溶液を一旦濃縮により除去し、その濃縮物を改めて含水エタノールで液液抽出する方が有利であることが明らかとなった。 As is apparent from Table 4, in order to efficiently purify and extract polymethoxyflavones and prevent turbidity when added to beverages, ethanol in the supercritical extract as in Example 1 was used. It has become clear that it is more advantageous to remove the solution once by concentration, and perform liquid-liquid extraction of the concentrate again with hydrous ethanol.
〔比較例2〕
工程Dの精製操作の有効性を確認するため、以下の対比実験を行った。
実施例1の「(5)ろ過」までと同様にポリメトキシフラボン類溶液を製造し、その後の「(6)濃度調整及び精製」において活性炭処理を行わずに5.1(w/w)%ポリメトキシフラボン類含有液を製造した。
この比較例2で製造したポリメトキシフラボン類含有液と、実施例1で製造したポリメトキシフラボン類含有液をそれぞれ常温で60日間保管し、経時的な沈殿発生の有無(目視評価)を観察して表5に示した。表中「0日」は製造直後のポリメトキシフラボン類含有液の状態を示したものである。
[Comparative Example 2]
In order to confirm the effectiveness of the purification operation in Step D, the following comparison experiment was performed.
A polymethoxyflavone solution was produced in the same manner up to “(5) Filtration” in Example 1, and 5.1 (w / w)% without performing activated carbon treatment in the subsequent “(6) Concentration adjustment and purification”. A liquid containing polymethoxyflavones was produced.
The polymethoxyflavone-containing liquid produced in Comparative Example 2 and the polymethoxyflavone-containing liquid produced in Example 1 are stored at room temperature for 60 days, and the presence or absence (visual evaluation) of occurrence of precipitation over time is observed. Table 5 shows the results. “0 day” in the table indicates the state of the polymethoxyflavone-containing liquid immediately after production.
表5から明らかなように、活性炭処理を行わない比較例2のポリメトキシフラボン類含有液では製造後5日目から沈殿の発生が見られた。安定なポリメトキシフラボン類含有液を製造するには活性炭処理の工程を設けることが有効であることが確認された。 As apparent from Table 5, in the polymethoxyflavone-containing liquid of Comparative Example 2 in which the activated carbon treatment was not performed, precipitation was observed from the fifth day after production. In order to produce a stable polymethoxyflavone-containing liquid, it has been confirmed that it is effective to provide an activated carbon treatment step.
〔実施例2〕
以下の表6の処方に従ってオレンジ飲料を調製した。
試飲したところ、異味異臭がなくオレンジの自然な風味が感じられた。
[Example 2]
An orange beverage was prepared according to the formulation in Table 6 below.
When tasting, there was no off-flavor and odor, and the natural flavor of orange was felt.
本発明の製造方法によれば、保存時の安定性が高く、また水への溶解性に優れたポリメトキシフラボン類をみかん属植物から効率よく且つ安価に得ることができる。 According to the production method of the present invention, polymethoxyflavones having high stability during storage and excellent solubility in water can be efficiently and inexpensively obtained from a mandarin plant.
Claims (8)
(A)超臨界流体と助溶媒による抽出操作によって、みかん属植物から抽出液Aを得る工程;
(B)濃縮操作によって、前記抽出液Aから助溶媒を除去した濃縮物Bを得る工程;
(C)エタノール水溶液による抽出操作によって、前記濃縮物Bから抽出液Cを得る工程;
(D)前記抽出液C又は前記抽出液Cにエタノール水溶液を添加した希釈溶液を多孔質素材で精製してポリメトキシフラボン類を得る工程;
を含む、水溶性ポリメトキシフラボン類の製造方法。 The following steps:
(A) A step of obtaining an extract A from a mandarin plant by extraction with a supercritical fluid and a cosolvent;
(B) The process of obtaining the concentrate B which removed the cosolvent from the said extract A by concentration operation;
(C) A step of obtaining an extract C from the concentrate B by an extraction operation with an aqueous ethanol solution;
(D) A step of purifying the extract C or a diluted solution obtained by adding an aqueous ethanol solution to the extract C with a porous material to obtain polymethoxyflavones;
A process for producing water-soluble polymethoxyflavones, comprising:
(A)超臨界流体と助溶媒による抽出操作によって、みかん属植物から抽出液Aを得る工程;
(B)濃縮操作によって、前記抽出液Aから助溶媒を除去した濃縮物Bを得る工程;
(C)エタノール水溶液による抽出操作によって、前記濃縮物Bから抽出液Cを得る工程;
(C1)濃縮操作によって、抽出液Cからエタノール及び水を除去した濃縮物C1を得る工程;
(D)前記濃縮物C1にエタノール水溶液を添加して希釈溶液を得た後、当該希釈溶液を多孔質素材で精製してポリメトキシフラボン類を得る工程;
を含む、水溶性ポリメトキシフラボン類の製造方法。 The following steps:
(A) A step of obtaining an extract A from a mandarin plant by extraction with a supercritical fluid and a cosolvent;
(B) The process of obtaining the concentrate B which removed the cosolvent from the said extract A by concentration operation;
(C) A step of obtaining an extract C from the concentrate B by an extraction operation with an aqueous ethanol solution;
(C1) A step of obtaining a concentrate C1 obtained by removing ethanol and water from the extract C by a concentration operation;
(D) A step of adding an aqueous ethanol solution to the concentrate C1 to obtain a diluted solution, and then purifying the diluted solution with a porous material to obtain polymethoxyflavones;
A process for producing water-soluble polymethoxyflavones, comprising:
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